U.S. patent number 8,604,246 [Application Number 12/741,655] was granted by the patent office on 2013-12-10 for single step catalytic preparation of para-aminophenol.
This patent grant is currently assigned to Centre National de la Recherche Scientifique (C.N.R.S.), Council of Scientific & Industrial Research, Vinati Organics Ltd (V.O.L.). The grantee listed for this patent is Abhay Deshpande, Francois Figueras. Invention is credited to Abhay Deshpande, Francois Figueras.
United States Patent |
8,604,246 |
Figueras , et al. |
December 10, 2013 |
**Please see images for:
( Certificate of Correction ) ** |
Single step catalytic preparation of para-aminophenol
Abstract
The method of using a bi-functional catalyst for the one-step
preparation of para-aminophenol. The catalyst includes a mixture of
a hydrogenation noble metal and a zirconium sulfate. Also, an
improved single-step process for the preparation of
para-aminophenol from nitrobenzene, in an aqueous medium, using the
bi-functional catalyst.
Inventors: |
Figueras; Francois (Lyons,
FR), Deshpande; Abhay (Lyons, FR) |
Applicant: |
Name |
City |
State |
Country |
Type |
Figueras; Francois
Deshpande; Abhay |
Lyons
Lyons |
N/A
N/A |
FR
FR |
|
|
Assignee: |
Centre National de la Recherche
Scientifique (C.N.R.S.) (Paris, FR)
Council of Scientific & Industrial Research (New Delhi,
IN)
Vinati Organics Ltd (V.O.L.) (Maharashtra,
IN)
|
Family
ID: |
39246840 |
Appl.
No.: |
12/741,655 |
Filed: |
November 7, 2008 |
PCT
Filed: |
November 07, 2008 |
PCT No.: |
PCT/EP2008/065100 |
371(c)(1),(2),(4) Date: |
October 29, 2010 |
PCT
Pub. No.: |
WO2009/060050 |
PCT
Pub. Date: |
May 14, 2009 |
Prior Publication Data
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|
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Document
Identifier |
Publication Date |
|
US 20110092740 A1 |
Apr 21, 2011 |
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Foreign Application Priority Data
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|
|
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Nov 7, 2007 [EP] |
|
|
07291339 |
|
Current U.S.
Class: |
564/418 |
Current CPC
Class: |
B01J
23/40 (20130101); B01J 27/053 (20130101); B01J
35/0006 (20130101); C01G 25/02 (20130101); C01G
55/00 (20130101); C07C 213/00 (20130101); C01G
25/06 (20130101); C07C 213/00 (20130101); C07C
215/76 (20130101) |
Current International
Class: |
C07C
213/02 (20060101); C07C 209/36 (20060101) |
Field of
Search: |
;564/418 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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1426964 |
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Jul 2003 |
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CN |
|
1559915 |
|
Jan 2005 |
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CN |
|
610549 |
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Oct 1948 |
|
GB |
|
1181969 |
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Feb 1970 |
|
GB |
|
61056158 |
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Mar 1986 |
|
JP |
|
Other References
Komatsu T et al, "Gas phase synthesis of para-aminophenol from
nitrobenzene on Pt/zeolite catalysts", Applied Catalysis A: General
, Nov. 25, 2004, pp. 95-102, vol. 276, No. 1-2, Elsevier Science,
Amsterdam , NL, XP004613245. cited by applicant .
Song Xet al, "Sulfated Zirconia-Based Strong Solid-Acid Catalysts:
Recent Progress" Catalysis Reviews: Science and Engineering, 1996,
pp. 329-412, vol. 38, No. 2, Marcel Dekker Inc. New York, US,
XP001536474. cited by applicant .
Zyuzin et al, "X-ray, Raman and FTIRS studies of t he
microstructural evolution of zirconia particles caused by the
thermal treatment", Journal of Solid State Chemistry, Oct. 1, 2006,
pp. 2965-2971, vol. 179, No. 10, Orlando, FL, US, XP005624309.
cited by applicant .
Cesario Franci Scodas Virgens et al, "Influence of the preparation
method of the textural properties of zirconia" Reaction Kinetics
and Catalysis Letters, Jan. 1, 2005, pp. 183-188, vol. 84, No. 1,
Kluwer Academic Publishers, DO, XP019265328. cited by applicant
.
Liu , Qiyong et al, "Process for Production of Superfine Zirconia
", 2005, XP002489261, Abstract. cited by applicant .
Chen, Ling, et al, "Method for Preparing Zirconium Oxide Nanopowers
by Ultrasonic Sol-Gel Process", 2005, XP002489262, Abstract. cited
by applicant .
International Search Report in Corresponding Application PCT/
EP2008/065100 dated Jun. 4, 2009. cited by applicant.
|
Primary Examiner: Davis; Brian J
Attorney, Agent or Firm: Young & Thompson
Claims
The invention claimed is:
1. A method of forming para-aminophenol in a one step reaction,
comprising: performing hydrogenation of nitrobenzene to
para-aminophenol in the presence of a bi-functional catalyst,
wherein the bi-functional catalyst comprises a mixture of a
hydrogenation noble metal and zirconium sulfate.
2. The method according to claim 1, wherein the hydrogenation noble
metal is selected from the group consisting of platinum, palladium,
ruthenium, nickel and mixtures thereof.
3. The method according to claim 1, wherein the hydrogenation noble
metal is platinum.
4. The method according to claim 1, wherein the hydrogenation noble
metal is supported on a support selected from the group consisting
of carbon, sulphated zirconia, zirconia, titanium dioxide,
sulphated titanium dioxide, alumina, silica, mixed oxides of
magnesium and lanthane, and mixtures thereof.
5. The method according to claim 1, wherein the zirconium sulfate
is Zr(SO.sub.4).sub.2(H.sub.2O).sub.4.
6. The method according to claim 1, wherein the zirconium sulfate
presents a specific surface area of between 2 m.sup.2/g and 300
m.sup.2/g.
7. The method according to claim 1, wherein the bi-functional
catalyst comprises a mixture selected from the group consisting of
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4+Pt/C,
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4+Pt/ZrS,
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4+Pt/ZrO.sub.2,
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4+Pt/TiO.sub.2,
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4+Pt/Al.sub.2O.sub.3,
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4+Pt/SiO.sub.2,
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4+Pt/MgLaO, and mixtures
thereof.
8. The method according to claim 1, wherein the weight ratio of
zirconium sulfate to the hydrogenation noble metal ranges from
100:1 to 1:100.
9. A process for the preparation of para-aminophenol comprising the
following steps: A) contacting a mixture of nitrobenzene and water
with a bi-functional catalyst comprising a mixture of a
hydrogenation noble metal and zirconium sulfate; B) placing the
reaction mixture under hydrogen pressure; C) allowing a reaction to
take place; D) terminating the reaction to obtain a reaction
mixture containing para-aminophenol; and E) isolating and
recovering the para-aminophenol from the reaction mixture.
10. The process according to claim 9, wherein the hydrogenation
noble metal is selected from the group consisting of platinum,
palladium, ruthenium, nickel and in mixtures thereof.
11. The process according to claim 9, wherein the hydrogenation
noble metal is supported platinum selected from the group
consisting of Pt/C, Pt/ZrS, Pt/ZrO.sub.2, Pt/TiO.sub.2,
Pt/Al.sub.2O.sub.3, Pt/SiO.sub.2, Pt/MgLaO, and mixtures
thereof.
12. The process according to claim 9, wherein the volume ratio of
water/nitrobenzene is between 50:1 to 1:50.
13. The process according to claim 9, wherein the reaction mixture
further comprises DMSO.
14. The process according to claim 9, wherein the zirconium sulfate
is Zr(SO.sub.4).sub.2(H.sub.2O).sub.4.
15. The process according to claim 9, wherein the zirconium sulfate
presents a specific surface area of between 2 m.sup.2/g and 300
m.sup.2/g.
16. The process according to claim 9, wherein the bi-functional
catalyst comprises a mixture selected from the group consisting of
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4+Pt/C,
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4+Pt/ZrS,
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4+Pt/ZrO.sub.2,
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4+Pt/TiO.sub.2, Zr
(SO.sub.4).sub.2 (H.sub.2O).sub.4+Pt/Al.sub.2O.sub.3,
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4+Pt/SiO.sub.2,
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4+Pt/MgLaO, and mixtures
thereof.
17. The process according to claim 9, wherein the weight ratio of
zirconium sulfate to the hydrogenation noble metal ranges from
100:1 to 1:100.
18. The process according to claim 9, wherein the volume/weight
ratio of nitrobenzene/zirconium sulfate is between 1 and 50.
19. The process according to claim 9, wherein the hydrogen pressure
is between 1 and 50 bars.
20. The process according to claim 9, wherein the temperature of
the reaction is in the range of 10.degree. C. to about 200.degree.
C.
Description
The present invention relates to the use of a bi-functional
catalyst for the one-step preparation of para-aminophenol. The
present invention also relates to an improved single step
bi-functional catalysis process for the preparation of
para-aminophenol. More particularly the process relates to the
preparation of para-aminophenol from nitrobenzene, in an aqueous
medium, using a bi-functional and eco-friendly catalyst.
para-Aminophenol ("p-aminophenol" or "PAP" in the following
specification) is a well known and very useful industrial chemical.
It is for example used as an intermediate in the production of
pharmaceuticals such as paracetamol, in the production of dyestuffs
such as sulphur dyes, and in making photographic chemicals.
The synthesis of paracetamol by acylation of p-aminophenol with
acetic acid has been for example reported in U.S. Pat. No.
6,215,024. The most difficult step is the synthesis of PAP. This is
industrially achieved in two steps: hydrogenation of nitrobenzene
to phenylhydroxylamine, followed by the isomerisation into PAP.
Conventionally, PAP is prepared by hydrolysing
para-nitrochlorobenzene to para-nitrophenol. Hydrogenation of
para-nitrophenol to PAP is then carried out using a Fe/HCl
catalyst. This multi-step process requires a quite large quantity
of iron (catalyst precursor). Consequently, the production of
iron-iron oxide sludge is large, creating serious effluent
problems. The work-up of the reaction crude is cumbersome. The
quantity of iron used is very important for the faster reduction
rate.
An important commercial process for the preparation of
para-aminophenol involves the catalytic hydrogenation of
nitrobenzene ("NB") in acidic medium using supported platinum-based
catalysts. In this process phenylhydroxylamine ("PHA") is first
formed and this intermediate immediately rearranges, in the
presence of acid, to PAP, according the well known Bamberger
rearrangement. However, under these conditions, a significant
amount of aniline as by-product is formed.
A first improvement was presented by Rylander et al. (DE 2118334),
based on the inhibition of the concurrent reaction of aniline
formation by the addition of dimethylsulphoxide (DMSO) to the
reaction medium containing nitrobenzene and a Pt/C catalyst (5%
Pt). The reaction performed in a solution of sulphuric acid
(H.sub.2SO.sub.4) yields PAP.
A recent work by Ryong Ryoo et al. (Stud. Surf. Sci. Cat., 135,
(2001), 4710) reported that a 5% Pt on mesoporous carbon of high
surface area was advantageous and permitted to reach 72%
selectivity into PAP and 81% conversion of nitrobenzene, in a
reaction performed in a solution of H.sub.2SO.sub.4. The kinetics
of this reaction have been studied and modelled by Rode, Vaidya and
Chaudhari (Org. Proc. Res. Devel., 3(6), (1999), 465-470).
Caskey et al. (EP 85890 and EP 85511), replaced DMSO by
diethylsulphide, with the same Pt/C catalyst, and performed the
reaction in two steps: the first at 18-20.degree. C., in the
presence of DMS O and NH.sub.3; the second consisted in the
isomerisation of phenylhydroxylamine by H.sub.2SO.sub.4 at
70.degree. C. The selectivity into PAP reached 90%.
Lee et al. (U.S. Pat. No. 4,885,389) reported the use of organic
acids, with relatively low results. Medcalf (U.S. Pat. No.
4,051,187) reports the use of rhodium catalysts. Le Ludec (U.S.
Pat. No. 3,927,191) reported the selective hydrogenation of nitro
aromatics into hydroxylamines in the presence of basic additives
such as pyridine. Sharma (U.S. Pat. No. 5,166,435) used phosphines
or phosphites to selectively hydrogenate nitroaromatics to
hydroxylamines.
Dunn (U.S. Pat. No. 4,264,529) has reported the use of platinum on
.gamma.-alumina in conjunction with sulphuric acid for the
hydrogenation of nitrobenzene to yield PAP. Derrenbacker (U.S. Pat.
No. 4,307,249) added a surfactant to the reaction medium in order
to increase the gas-liquid interface. Klausener (U.S. Pat. No.
5,545,754) used a reaction mixture containing sulphuric acid and a
miscible organic solvent.
The first attempt to use pure heterogeneous catalysis for the
conversion of nitrobenzene into p-aminophenol is due to Chaudhari
et al. (U.S. Pat. No. 6,028,227), who used a platinum catalyst
supported by a solid acid consisting of an acid resin. The
preparation of p-aminophenol is achieved in one single step.
However if the nitrobenzene conversion was high (97%), the
selectivity of PAP was low (15%), and that of aniline 85%. The
authors claimed many solid acids selected from the group consisting
of ion exchange resins, heteropolyacids, synthetic and natural
acidic clays, and acidic zeolites mainly silico-aluminates and
zeolites. Using a nickel catalyst, the conversion was reduced to
14%, and the selectivity to 14%. The same authors also reported the
selective hydrogenation of nitrophenol into PAP (Org. Proc. Res.
Dev., 7, (2003), 202).
Komatsu et al (Applied Catalysis, 2004, 276, 95-102) have reported
a process in gaseous phase for the synthesis of p-aminophenol by
using a solid catalyst consisting of metal particles supported on
acidic zeolites. By using H-ZSM-5 zeolite the selectivity is of
66%. However, aniline and o-aminophenol are defined to be
by-products of the reaction.
All attempts reported up to now to use heterogeneous catalysis are
disappointing since the yields and selectivities are low. The
catalysts used for hydrogenation of nitrobenzene to p-aminophenol
reported in the literature are Pt, Pd, Ru, and PtO.sub.2. Among
these catalysts, however, Pt is the most active for this system but
it is very costly. All these being noble metal the process becomes
cost intensive. It also demands to use the same catalyst for
several times and also to recover the metal from deactivated
catalyst in order to make the process economical.
Moreover, in these processes, the inherent drawback is the use of
excess sulphuric acid that requires neutralisation to produce
enormous amounts of salt at the end of the reaction. The reaction
medium is thus highly corrosive and it is necessary to use a
special steel reactor.
A first objective of the present invention is to provide a
bi-functional catalyst for use in a single step process of
hydrogenation of nitrobenzene (NB) to phenylhydroxylamine and
isomerisation to para-aminophenol (PAP) with a high NB conversion
rate and a high selectivity to PAP.
Another objective of the invention relates to a single step process
for the preparation of p-aminophenol using bi-functional
heterogeneous catalysis, in which dilute sulphuric acid is replaced
by a solid acid.
Song et al (Catalysis Review: Science and Engineering, 1996, 38(2),
329-412) reported the use of zirconium sulphate as a solid catalyst
for the replacement of sulphuric acid solution. Nevertheless the
authors do not report the use of such catalyst for the one step
reaction of nitrobenzene to para-aminophenol.
Another objective is to increase the selectivity to
para-aminophenol and to maintain a high conversion of
nitrobenzene.
The present invention aims also at providing a catalyst with a low
hydrogenation noble metal content, e.g. a low platinum content, and
at using a non corrosive reaction medium, thereby avoiding the use
of special steel for the reactor, and at using an environmental
friendly and cheap solvent.
Still another objective is to use an acid catalyst which is easy to
prepare and regenerate.
Further objectives will appear in the following description of the
present invention. All the above-mentioned objectives are met in
all or in part with the present invention.
As a first object, the present invention provides the use of a
bi-functional catalyst for the one step reaction of nitrobenzene to
para-aminophenol, wherein the bi-functional catalyst comprises a
mixture of hydrogenation noble metal with zirconium sulfate.
The inventors have now discovered that the preparation of PAP from
nitrobenzene (NB) provides good conversion of NB and good
selectivity of PAP when using a specific solid acid catalyst, which
comprises a supported hydrogenation noble metal and zirconium
sulfate.
Indeed, zirconium sulfate has been found by the inventors to be
catalytically active for the isomerisation of phenylhydroxylamine
to PAP, while the hydrogenation noble metal is known to catalyse
the hydrogenation reaction of NB to phenylhydroxylamine.
According to a feature of the invention, supported hydrogenation
noble metal and zirconium sulfate are present as catalyst in the
reaction medium in the form of a mixture. The expression "mixture"
indicates a mechanical mixture and means that the hydrogenation
noble metal and the zirconium sulfate are added separately, or as
pre-mix to the reaction medium.
Carbon-supported zirconium sulfate has been described as an
efficient water tolerant solid acid catalyst for esterification
reactions (Catalysis Letters, vol 117, no 3-4, September 2007).
Zirconium sulfate has also been used to promote support materials
consisting of Al.sub.2O.sub.3 on which noble metal from the
platinum group are deposited in order to prepare high performance
catalysts used in method for oxidizing a gas stream as described in
US 2004/0028589.
Zirconium sulfate may be purchased or prepared according to a
process which will be further described in the following
specification. This process is also part of the present
invention.
Zirconium sulfate for use in the present invention preferably is in
crystallized form and presents a specific surface area of between 2
m.sup.2/g and 300 m.sup.2/g, preferably between 2 m.sup.2/g and 100
m.sup.2/g, more preferably between 2 m.sup.2/g and 50 m.sup.2/g,
for example about 3.5 m.sup.2/g to 10 cm.sup.2/g.
The pore volume of the zirconium sulfate is generally greater than
or equal to 0.6 cm.sup.3/g, preferably greater than or equal to 0.2
cm.sup.3/g, more preferably greater than or equal to 0.25
cm.sup.3/g. Its average pore diameter is generally greater than or
equal to 20 .ANG.ngstroms, preferably greater than or equal to 30
.ANG.ngstroms.
All above characteristics are measured using known methods in the
art. As such, surface area is measured using a BET analysis of the
isotherms of adsorption of nitrogen, pore volume corresponds to the
volume adsorbed at P/P0=0.98 and pore diameter is determined by
analysis of the isotherm using BJH theory as disclosed for example
in "The Determination of Pore Volume and Area Distributions in
Porous Substances. I. Computations from Nitrogen Isotherms",
Elliott P. Barrett, Leslie G. Joyner, and Paul P. Halenda, J. Am.
Chem. Soc., 73(1), (1951), 373-380.
Advantageously, although not necessary, zirconium sulfate is
activated by calcination prior use. Temperatures of calcination
range from 400.degree. C. to 700.degree. C., preferably from
450.degree. C. to 650.degree. C., for example about 550.degree. C.
Calcination is conducted in air, most preferably with a temperature
increase of 1-2.degree. C./min.
Berk et al (GB 610,549) reported the preparation of basic zirconium
sulphate by dissolving a zirconium source in a solution of
sulphuric acid.
Zirconium sulfate may be obtained by dissolving zirconia (either
commercially available or prepared as defined below) or zirconium
salts for example chosen from among zirconyl chloride or
oxycloride, zirconium acetate, zirconium alkoxides and the like, in
a concentrated solution of sulphuric acid (e.g. 1N aqueous
solution). Zirconia may for example be immersed into the acidic
solution, stirred for a few minutes, preferably 5 to 30 minutes,
for example 15 minutes until complete dissolution.
The ratio zirconia/sulphuric acid may vary, in general an excess of
sulphuric acid is used. Satisfactory results were obtained by
contacting 1 g zirconia with 15 mL 1N sulphuric acid.
The zirconium sulfate is then filtered off and washed several times
with demineralised water, and dried in an oven (about
80-120.degree. C.) overnight.
Finally, the zirconium sulfate is sieved to a specific diameter
size, generally from 60 to 100 mesh, for example about 80 mesh and
optionally calcined at the desired temperature, generally comprised
between 450.degree. C. and 750.degree. C., preferably between
500-700.degree. C., at a temperature rise of 1-2.degree.
C./min.
Fu et al (US 2005/0175525) reported a step of aging of the
precipitate at a temperature higher than 60.degree. C. in the
process of preparation of zirconia (ZrO.sub.2).
Zirconium sulfate may for example be prepared by dissolving
zirconia in sulphuric acid, which zirconia may be prepared
according to the following process comprising the steps of:
i) dissolving a zirconium dioxide (zirconia) precursor into
water;
ii) allowing the precursor to hydrolyse to give zirconia as a
precipitate, in a basic medium, generally at a constant pH greater
than or equal to 9, advantageously 10;
iii) aging the precipitate, at a temperature ranging from
50.degree. C. to 100.degree. C., preferably from 70.degree. C. to
90.degree. C.;
iv) isolating and washing with water the aged precipitate; and
v) drying, powdering and sieving the obtained zirconia.
In the above preparation process, the zirconia precursor may be of
any type known in the art, provided that it is transformed into
zirconium hydroxide when contacted with water, in a basic medium.
Such precursors may for example, be chosen from among zirconyl
chloride or oxychloride, zirconium acetate, zirconium
acetylacetonate, zirconium alkoxides, and the like.
Suitable bases that may be used to undergo the zirconia precursor
hydrolysis are advantageously strong organic or inorganic,
preferably inorganic, bases, so that the pH of the reaction medium
is equal to or greater than 9, preferably 10. Examples of such
bases are, but not limited to, ammonium hydroxide, sodium or
potassium hydroxides, mixtures thereof and the like.
The hydrolysis product is then aged overnight at a temperature
ranging from 50.degree. C. to 100.degree. C., preferably from
70.degree. C. to 90.degree. C., for example 80.degree. C. The
precipitate is then isolated, according to conventional methods
(filtration, centrifugation, and the like) and washed several times
with hot water.
In step v), the precipitate is dried, for example in an oven, at a
temperature ranging from 50.degree. C. to 100.degree. C.,
preferably from 70.degree. C. to 90.degree. C., for example
80.degree. C. for 1 to 3 days, e.g. 36-48 hours. Finally zirconia
is powdered, generally ground in a mortar, and sieved to a diameter
size, preferably ranging from 60 to 100 mesh, typically about 80
mesh, according to known methods.
The present invention therefore also relates to a process for the
preparation of zirconium sulfate, comprising the steps of:
a) dissolving a zirconium dioxide (zirconia) precursor into
water;
b) allowing the precursor to hydrolyse to give zirconia as a
precipitate, in a basic medium, generally at a constant pH greater
than or equal to 9, advantageously 10;
c) aging the precipitate, at a temperature ranging from 50.degree.
C. to 100.degree. C., preferably from 70.degree. C. to 90.degree.
C.;
d) isolating and washing with water the aged precipitate;
e) contacting the resulting hydrated zirconia with sulphuric
acid;
f) dissolving the precipitate in the acidic medium;
g) removing water from the reaction medium, until a precipitate of
zirconium sulfate is formed; and
h) drying the obtained zirconium sulfate.
In the above preparation process, the zirconia precursor may be of
any type known in the art, as previously described. Suitable bases
that may be used to undergo the zirconia precursor hydrolysis are
also as depicted above.
In step e), the precipitate is contacted with an appropriate amount
of sulphuric acid, generally about 1 mL of concentrated sulphuric
for about 1 to 2 g of hydrated zirconia. The mixture is
advantageously stirred until dissolution of the precipitate. A
complete dissolution is compulsory, and when most of the
precipitate is dissolved a turbid solution is obtained.
After complete, dissolution, water is removed from the solution,
e.g. in a rotary evaporator, at a temperature of about 80.degree.
C., until a precipitate is obtained. The precipitated zirconium
sulfate is collected and dried, at a temperature of about
120.degree. C., during a couple of hours, say 5-24 hours, e.g.
10-18 hours.
Finally the zirconium sulfate may be activated by calcination in
flowing air under conventional conditions known by the skilled in
the art of solid catalysts, e.g. at a temperature of between
450.degree. C. and 750.degree. C., prefer ably 500.degree. C. and
700.degree. C., more preferably 550.degree. C. and 650.degree. C.,
advantageously at a temperature of about 625.degree. C., for 2 to 8
hours, for example 4 hours.
The zirconium sulfate obtained from the above described process is
particularly suitable for the single step preparation of PAP from
NB, which will be further described in this specification.
As previously disclosed, zirconium sulfate is used in the process
of the present invention as a catalyst together with a
catalytically amount of a hydrogenation noble metal.
The expression "hydrogenation noble metal" means any noble metal
known in the art for catalytic hydrogenation reaction, and
preferably those conventionally used in the hydrogenation process
of nitrobenzene (NB) to phenyl hydroxylamine (PHA).
"Hydrogenation noble metal" therefore includes platinum, palladium,
ruthenium, platinum dioxide, nickel and the like, alone or in
mixtures. Preferably the "hydrogenation noble metal" used in the
process of the present invention, together with zirconium sulfate,
is chosen from platinum and palladium or mixtures thereof, more
preferably the "hydrogenation noble metal" is platinum.
The hydrogenation noble metal may be used as such, in any form
known in the art, such as powder. Preferably the hydrogenation
noble metal is used as a supported catalyst. In this case, the
present inventors have established that the support may be of any
type for the envisaged reaction of conversion of NB to PAP, i.e.
the nature of the support has no, or hardly no effect, on the
conversion rate and selectivity of said reaction.
Convenient supports for the hydrogenation noble metal may therefore
be of any type and be chosen, for example and as a non limiting
way, from among carbon, sulphated zirconia, zirconia, titanium
dioxide, sulphated titanium dioxide, alumina, silica, mixed oxides
of magnesium and lanthane, and the like, as well as mixtures of
such supports.
For example, when the hydrogenation noble metal is platinum, the
various types of supported platinum are referred to as Pt/C,
Pt/ZrS, Pt/ZrO.sub.2, Pt/TiO.sub.2, Pt/Al.sub.2O.sub.3,
Pt/SiO.sub.2, or Pt/MgLaO and mixtures thereof.
Such supported platinum may be prepared according known techniques,
such as for example those disclosed in J.-P. Brunelle, Pure &
Applied Chemistry, 50, (1978), 124; or C. Marcilly et J.-P. Franck,
Revue Institut Francais du Petrole, 39, (1984), 337. Additionally,
specific preparations of supported platinum on various supports are
presented in the examples that follow in the present
specification.
The amount of hydrogenation noble metal in the support may vary in
great proportions, depending on the characteristics of the
hydrogenation metal itself, and on the nature of the support. Such
usable amounts are known by the skilled in the art.
By way of illustration, and as a non limiting example, the content
of platinum in the supported catalyst ranges between 0.01 and 10%
by weight of the total weight of the supported catalyst, preferably
between 0.1-5% by weight, for example 0.1%, 0.2-2% or 5% by
weight.
The catalyst for use in preparing PAP from NB comprises, and
preferably consists of, a mixture of zirconium sulfate with a
supported hydrogenation noble metal. When the hydrogenation noble
metal is platinum, the catalyst for use in preparing PAP from NB
preferably is Zr(SO.sub.4).sub.2(H.sub.2O).sub.4+Pt/C,
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4+Pt/ZrS,
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4+Pt/ZrO.sub.2,
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4+Pt/TiO.sub.2,
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4+Pt/Al.sub.2O.sub.3,
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4+Pt/SiO.sub.2,
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4+Pt/MgLaO, and mixtures
thereof.
The weight ratio of zirconium sulfate to the hydrogenation noble
metal may also vary in great proportions, for example from 100:1 to
1:100, preferably from 100:1 to 1:10, more preferably from 75:1 to
1:5, advantageously from 50:1 to 1:2, keeping in mind that the
amount of hydrogenation catalyst (the hydrogenation noble metal)
should be as low as possible as compared to the amount of the
isomerisation catalyst (the zirconium sulfate).
Without any intention to be bound by theory, it is assumed that the
hydrogenation reaction and the isomerisation reaction compete
during the one-pot conversion of NB to PAP. While the first
reaction runs rather quickly, the second one is slower. If a too
high amount of hydrogenation catalyst is present, then the
hydrogenation reaction tends to further hydrogenate the
intermediate PHA to aniline, before the isomerisation reaction
could take place to convert PHA to PAP.
The skilled artisan will therefore be able to determine with
routine experiments, the appropriate ratio of hydrogenation noble
metal to zirconium sulfate. For example, when the catalyst used is
zirconium sulfate with 2% platinum supported on sulphated zirconia,
the weight ratio zirconium sulfate to platinum on sulphated
zirconia may range from 100:1 to 1:10, more preferably from 75:1 to
1:5, advantageously from 50:1 to 1:2. The following examples will
present some convenient usable ratios of zirconium sulfate to
supported platinum.
As an other example, when palladium is used in lieu of platinum,
the amount of palladium is about five- to thirty-fold greater,
since the activity of palladium is weaker as compared to that of
platinum for the herein-described process.
The present inventors have evidenced that the use of a mixture of
zirconium sulfate together with a hydrogenation noble metal, such
as supported platinum- or palladium-based catalyst, was very
efficient in terms of NB conversion and selectivity to PAP in the
preparation process of para-aminophenol starting from
nitrobenzene.
The present invention therefore provides, as a further object, a
one-step process for an environmentally friendly synthesis of PAP,
using heterogeneous acid catalysis. This process avoids the use of
sulphuric acid and the formation of sulphates, and requires only
very small amounts of hydrogenation noble metal. The catalyst
comprises a mixture of zirconium sulfate together with a
hydrogenation noble metal, such as platinum or palladium and the
like, as defined above.
The solvent is water and the selectivity for PAP reaches 95% or
more. The separation of products is simplified due to two factors:
the selectivity is high and no sulphur or amine additives are
required.
More particularly, the present invention provides a single step
process for the preparation of para-aminophenol comprising the
following steps: A) contacting a mixture of nitrobenzene and water
with a bi-functional catalyst comprising, and preferably consisting
of, a mixture of a hydrogenation noble metal with zirconium
sulfate; B) placing the reaction mixture under hydrogen pressure;
C) allowing the reaction to take place; D) terminating the reaction
to obtain a reaction mixture containing para-aminophenol; and E)
isolating and recovering para-aminophenol from the reaction
mixture.
The process of the present invention is detailed in the following
description, but is not limited to such details in any way.
The hydrogenation noble metal used in the above process is as
previously described in the present specification. Preferably, the
hydrogenation noble metal is platinum or palladium, supported or
not. According to a more preferred embodiment, the hydrogenation
noble metal is supported platinum and may for example be chosen
from Zr(SO.sub.4).sub.2(H.sub.2O).sub.4+Pt/C, ZrS+Pt/ZrS,
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4+Pt/ZrO.sub.2,
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4+Pt/TiO.sub.2,
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4+Pt/Al.sub.2O.sub.3,
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4+Pt/SiO.sub.2,
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4+Pt/MgLaO, and mixtures
thereof.
The process according to the invention comprises a first step A)
wherein nitrobenzene (NB) is mixed with water in a volume ratio
(water/NB) ranging from 50:1 to 1:50, preferably from 50:1 to 1:1,
still more preferably from 40:1 to 3:1.
Advantageously the volume ratio (water/NB) ranges from 15:1 to
3:1.
The process does not exclude the use of dimethylsulphoxide (DMSO),
as conventionally disclosed in the prior art (see for example
Rylander et al. U.S. Pat. No. 3,715,397) in order to improve
selectivity of PAP. However, the presence of DMSO in the reaction
mixture of the present process is not compulsory: good conversion
rates of NB as well as good selectivity of PAP have been obtained
without the use of DMSO.
When DMSO is present in the reaction mixture, the volume ratio
NB/DMSO generally ranges from 2:1 to 1:1. According to an
embodiment, DMSO is added to the reaction mixture. According to
another embodiment, no DMSO is used in the process of the present
invention.
Preparations of PAP from NB are also generally conducted in alcohol
solvents (see for example Rylander et al. U.S. Pat. No. 3,964,509).
However, alcohols are not suitable for the process of the present
invention, since they may have a deleterious action on the solid
acid catalyst used therein.
Mention may also be made of the use of surfactants (for example as
disclosed in U.S. Pat. No. 3,383,416) in the reaction mixture, for
improving the surface of exchange between the solid catalyst
(hydrogenation noble metal) and the liquid phase, and consequently
accelerate the whole reaction process. Such use is however not
preferred, although possible, since the complete removal of the
surfactants from the obtained product (PAP) is a rather tedious
operation.
The mixture of nitrobenzene, water, and optionally DMSO, is added
with the mixture of hydrogenation noble metal with zirconium
sulfate as previously described.
When platinum is the hydrogenation noble metal, the NB/platinum
ratio (volume/Pt weight) is generally comprised between 1 and 600,
preferably between 10 and 300, more preferably between 15 and 150,
for example 15, 30, 45, 50 or 60, advantageously 60.
The ratio NB/zirconium sulfate (volume/weight) is generally
comprised between 1 and 50, preferably between 2 and 30, more
preferably between 3 and 15, for example 3, 6, 9 or 15.
The reaction medium is then placed under conventional hydrogenation
conditions, such as for example in an autoclave under a hydrogen
pressure ranging from 1 to 50 bars, preferably from 2 to 35 bars,
more preferably from 3 to 20 bars, generally under hydrogen
pressure of 10 bars. The reaction temperature may vary in the range
10.degree. C. to about 200.degree. C. depending on the kinetics of
the reaction. Preferably the reaction temperature is set in the
range of 50-100.degree. C., for example 80.degree. C.
Depending on the hydrogen pressure, the reaction temperature, and
the amount of reagents and catalysts, the reaction may be run for a
period of 10 minutes to 8 hours, generally for a period of 2 to 7
hours.
The progress of the reaction is monitored by taking and analysing
samples from the reaction mixture. After completion of the
reaction, the reaction mixture is removed from the autoclave, and
the solid catalyst is separated from the liquid using conventional
techniques, such as filtration for example. The filtrate is then
extracted according to usual methods known by the skilled artisan,
e.g. with organic solvents chosen from the group comprising
toluene, cyclohexane, ethyl acetate or the like.
After extraction of the reaction mixture with an organic solvent
and the separation of the aqueous layer, the latter is treated with
an ammonia solution to adjust the pH of solution to 3-4, where PAP
is precipitated partly. The solid thus obtains is separated by
filtration. Again the filtrate is extracted with the organic
solvent and aqueous layer is treated with ammonia solution to pH
7-8 to substantially precipitate PAP. The total solid thus obtained
after the first and second extractions is washed with distilled
water, dried and weighed.
Depending on the various embodiments of the process of the present
invention, conversion of nitrobenzene ranges between 30-97%, and
selectivity of para-aminophenol ranges between 60-99%.
The invention is further described with the help of the following
examples which are given as illustrative purpose only and which do
not intend to limit the scope of the invention in any way.
EXPERIMENTAL PART
Part A: Preparation of Catalysts
Example A1
Preparation of Zirconia
48 g of zirconyl chloride (ZrOCl.sub.2.XH.sub.2O, MW: 322.249) are
dissolved in 375 mL water. The precipitation is carried out in a 3
L round bottomed flask, equipped with a mechanical stirrer and pH
electrode for the online pH measurement.
Demineralised water (500 mL) is added to the flask initially so
that the agitator and the tip of pH electrode dip in water. pH is
adjusted at 10 by adding ammonium hydroxide solution.
Zirconium hydroxide is precipitated at constant pH=10 with the help
of ammonium hydroxide. The zirconyl chloride solution is added to
the precipitator at a rate of 15 mL/min and the pH is maintained at
10 with the help of addition of ammonium hydroxide solution (100 mL
of concentrated ammonia (30%), diluted to 500 mL with demineralised
water), throughout the addition. Both these solutions are added to
the flask with the help of peristaltic pumps.
After completion, the precipitate is aged at 80.degree. C. for 12 h
after which, it is separated by centrifugation or filtration and
washed 5 times with 800 mL of hot water (80.degree. C.) to remove
the excess ammonia and chloride ions. The precipitate is then
transferred to a glass pan and dried in oven at 80.degree. C. for
36-48 h. After drying, the solid is grinded and sieved to 80 mesh
before storing.
Example A1
Preparation of Platinum on Sulphated Zirconia or Sulphated Titanium
Dioxide: (General Method)
A stock solution is prepared by dissolving 1 g of chloroplatinic
acid (H.sub.2PtCl.sub.6.xH.sub.2O; M.W.: 409.82) in 100 mL
demineralised water. Appropriate amount of this solution
(corresponding to the desired platinum loading in the solid) is
transferred to a round bottomed flask.
Ammonium hydroxide solution corresponding to 1.5-2 times the
stoechiometric requirement is added to this flask and immersed in
an oil bath maintained at 80.degree. C.
The light brownish yellow colour of the solution disappears in
10-15 min. After the colour disappears, the temperature of the oil
bath is increased so as to boil off excess ammonia.
After the ammonia is completely removed (test with wet pH paper),
the solution is cooled to room temperature and desired amount of
support (sulphated zirconia or sulphated titania) is added to the
flask.
The slurry is stirred for 15 min and immersed in an oil bath
maintained at 110.degree. C. to boil off water. The residual solid
is transferred to a glass pan with a minimum quantity of
demineralised water and dried in oven at 80.degree. C. overnight.
The dry solid is sieved and filled in bottle.
Before use, the catalyst is calcined at 400.degree. C. for 4 h in a
current of air, with a temperature rise of 1-2.degree. C./min.
After returning to room temperature, the air is replaced by
nitrogen and purged for 10-15 min so as to displace the air
completely. Nitrogen is then replaced by hydrogen and the catalyst
is reduced at 250.degree. C. for 2 h, with a temperature rise of
1-2.degree. C./min.
After returning to room temperature, the hydrogen is again replaced
with nitrogen and purged for 10-15 min. The catalyst is then
transferred to an air tight bottle with minimum exposure to
air.
The supported platinum catalyst can be also reduced directly
without any calcination, and appears to be more active in that
case.
Example A2
Preparation of 2% Platinum Supported on Sulphated Zirconia:
(Specific Example)
1 g of H.sub.2PtCl.sub.6.6H.sub.2O (M.W.: 409.82) is dissolved in
100 mL demineralised water. 10.6 mL of the above solution is taken
in a 50 mL round bottom flask. 10 mL demineralised water and
.about.10 mL ammonia solution is added to it and the solution is
stirred in an oil bath at 80.degree. C. for 15-20 min.
At the end of this, the solution, which is originally yellow in
colour, becomes colourless. Even after the disappearance of the
yellow colour, presence of ammonia could be tested with the help of
a wet pH indicator paper. The temperature of the oil bath is then
increased to 114.degree. C. so as to facilitate the removal of
excess ammonia. Complete removal of ammonia is confirmed with the
help of a wet pH indicator paper. The solution is finally allowed
to cool to room temperature.
2 g sulphated zirconia, previously calcined at 650.degree. C. for 4
h, are added to the cooled solution and the slurry is stirred for
10-15 min. The flask is then immersed in an oil bath maintained at
110.degree. C. so as to evaporate water. Solid thus obtained is
transferred to a glass petry dish with the help of minimal
demineralised water. The solid is then dried in an oven at
80.degree. C., overnight.
The dry catalyst thus obtained is calcined at 400.degree. C. for 4
h in a current of air (100 mL/min). The temperature programme used
for the furnace is, 0 h--25.degree. C.; 7 h--400.degree. C.; 11
h--400.degree. C.; 11.5 h--25.degree. C. The furnace temperature is
allowed to reach 25.degree. C. at the end without disturbing the
assembly.
Air is then replaced by nitrogen for 10-15 min followed by hydrogen
(50 mL/min), and the catalyst is reduced at 250.degree. C. for 2 h.
The temperature programme used for the furnace is, 0 h--25.degree.
C.; 4 h--250.degree. C.; 6 h--250.degree. C.; 11.5 h--25.degree. C.
The furnace temperature is allowed to reach 25.degree. C. at the
end without disturbing the assembly.
The hydrogen is finally replaced by nitrogen (100 mL/min) for 10-15
min. The reduced catalyst was then transferred to an airtight
bottle with minimal exposure to atmosphere.
Here also the supported platinum catalyst can be reduced directly
without calcination, following the same reduction procedure.
Example A3
Preparation of MgLaO
The following two solutions were prepared:
Solution A:
TABLE-US-00001 Magnesium nitrate hexahydrate: 99 g (0.386 mol)
Lanthanum nitrate hydrate: 42 g (0.129 mol) Demineralised water:
500 ml
Solution B:
TABLE-US-00002 Potassium hydroxide: 56 g (1.0 mol) Potassium
carbonate: 36 g (0.26 mol) Demineralised water: 520 ml
The precipitation is carried out in a 3 L round bottomed flask,
equipped with a mechanical stirrer and pH electrode for the online
pH measurement.
500 mL demineralised water is added to the flask initially so that
the agitator and the tip of pH electrode dip in water. pH of this
water is adjusted at 10 by adding requisite amount of solution
B.
The precipitation was carried out at pH 10, with solution A being
added at a rate of 25 mL/min and the rate of addition of solution B
adjusted accordingly.
After the precipitation was complete, the slurry was aged at
80.degree. C. for 12-15 h. The slurry was then filtered and the
precipitate was washed with demineralised water 4-5 times. After
water washes, the precipitate was washed with methanol two
times.
The precipitate was finally transferred to a drying tray and dried
overnight at 80.degree. C. The dry solid was crushed to powder with
a spatula and sieved to 80 mesh.
The powder thus obtained was calcined in a stream of air (100
mL/min) at 650.degree. C. for 4 h, with temperature rise of
1-2.degree. C./mi n.
Example A4
Preparation of Platinum on Zirconia, Titanium Dioxide or MgLaO
(General Method)
A stock solution is prepared by dissolving 1 g of chloroplatinic
acid (H.sub.2PtCl.sub.6.xH.sub.2O; M.W.: 409.82) in 100 mL
demineralised water. Appropriate amount of this solution
(corresponding to the desired platinum loading in the solid) is
transferred to a round bottomed flask.
Desired amount of support (zirconia, titanium dioxide (=titania) or
MgLaO-3) is added to the flask. The slurry is stirred for 15 min
and immersed in an oil bath maintained at 110.degree. C. to boil
off water. The residual solid is transferred to a glass pan with a
minimum quantity of demineralised water and dried in oven at
80.degree. C. overnight. The dry solid is sieved to 80 mesh and
filled in bottle.
Before use, the catalyst is calcined at 400.degree. C. for 4 h in a
current of air, with a temperature rise of 1-2.degree. C./min.
After returning to room temperature, the air is replaced by
nitrogen and purged for 10-15 min so as to displace the air
completely. Nitrogen is then replaced by hydrogen and the catalyst
is reduced at 250.degree. C. for 2 h, with a temperature rise of
1-2.degree. C./min.
After returning to room temperature, the hydrogen is again replaced
with nitrogen and purged for 10-15 min. The catalyst is then
transferred to an air tight bottle with minimum exposure to
air.
Example A5
Preparation of Zirconium Sulfate: (According to the Invention)
48 g zirconyl chloride (ZrOCl.sub.2.XH.sub.2O, MW: 322.249) are
dissolved in 375 mL water. Zirconium hydroxide is precipitated at
constant pH=10 with the help of ammonium hydroxide.
The precipitate is aged at 80.degree. C. for 12 h after which, it
is separated by centrifugation and washed several times with hot
water to remove the excess ammonia and chloride ions.
The wet precipitate is transferred to a conical flask. The
centrifuge bottles are rinsed with 3-4 installments of water (total
200 mL). A solution of 21 mL concentrated sulphuric acid in 150 mL
water is prepared and added to the conical flask. Slurry is stirred
for 1 h at room temperature. Within this time, most of the
precipitate dissolved and a turbid solution is obtained.
The turbid solution thus obtained is fed to a rotary evaporator and
water is evaporated. The water bath is maintained at 80.degree. C.
during the evaporation. The solution becomes completely clear at
higher temperature during the evaporation and remains so till the
end. At the end, a white precipitate appears almost
instantaneously. The evaporation is continued for 15-20 minutes
after this.
The precipitate is then transferred to a glass pan with the help of
minimum amount of ethanol and dried overnight at 120.degree. C.
After drying, the precipitate appears to be still a bit wet.
The zirconium sulfate thus obtained is calcined at a ramp of
1-2.degree. C./min up to the desired temperature, maintained for 4
h.
Example B1
Using 2% Pt/Zro.sub.2 and Zirconium Sulfate of Example A5
75 mL water and 3 mL nitrobenzene (NB) are taken into a 100 mL
capacity autoclave equipped with an efficient gas induction
agitator, temperature sensor, sampling tube and a baffle.
0.01 g of 2% Pt/ZrO.sub.2 (from MELCAT, ref F20922/1) and 0.5 g of
zirconium sulfate obtained at Example A5
(Zr(SO.sub.4).sub.2(H.sub.2O).sub.4-A5), previously calcined at
650.degree. C. for 4 h, are added and the reactor is closed.
Nitrogen is fed to the reactor (2.5 bar) and purged three times.
Nitrogen is then replaced with hydrogen (10 bar) and purged three
times. The agitation is started and maintained at 1200 rpm.
Finally, the autoclave is heated to 8.degree. C., with hydrogen
pressure of 10 bar. Samples are then periodically withdrawn to
monitor progress of reaction. The reaction is usually run for 7
hours.
The autoclave is allowed to cool to room temperature and then back
to atmospheric pressure. The reaction mixture is removed, diluted
in ethanol, and the composition of the products determined by HPLC
using a UV detection.
Under the above conditions, preparation of PAP from NB was achieved
with a NB conversion of 97% after 4 h of reaction, and a PAP
selectivity of 76%.
Conversion and selectivity are determined from the chemical
analyses of the reaction medium by the usual equations:
conversion=moles of nitrobenzene reacted/moles of initial
nitrobenzene; and selectivity=moles of PAP(or PHA or AN)/moles of
nitrobenzene reacted.
A similar experiment was conducted in a 700 mL capacity reactor
with 56 mL nitrobenzene (NB) and 490 mL water (ratio water/NB=7.3).
0.14 g of 2% PT/ZrO.sub.2 and 7 g of zirconium sulfate obtained at
example A5 were added and the temperature was heated to 80.degree.
C. under hydrogen pressure of 20 bar.
Under the above conditions, preparation of PAP from NB was achieved
with a NB conversion of 96.1% after 8 h of reaction and a PAP
selectivity of 81.1%.
A similar experiment was conducted using DMSO (2 mL) together with
water and NB. In that case, 99% conversion and 80% selectivity were
obtained.
Other experiments were carried out, without DMSO, using a mixture
Pt/ZrS reduced at 250.degree.
C.+Zr(SO.sub.4).sub.2(H.sub.2O).sub.4, leading to similar
results.
Similar selectivity could be reached using either Pt/ZrO.sub.2 (not
sulphated), Pt/TiO.sub.2 or Pt/MgLaO mixed with zirconium sulfate
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4-A5. With the mixture 2%
Pt/ZrO.sub.2 (0.01 g)+Zr(SO.sub.4).sub.2(H.sub.2O).sub.4 (0.5 g) at
80.degree. C. and 10 bars hydrogen (H.sub.2) the conversion reaches
81% and the selectivity to PAP 71%. Similar results have been
obtained with Pt/TiO.sub.2 and Pt/MgLaO showing that the support of
platinum has no critical effect.
This is confirmed by the results obtained with a commercial Pt/C
containing 1% Pt, as illustrated by the following experiments
performed in the standard conditions (3 mL nitrobenzene, 75 mL
water, temp 80.degree. C.). Using as catalyst a mixture of 0.01 g
1% Pt/C+1.0 g Zr(SO.sub.4).sub.2(H.sub.2O).sub.4-A5 and 10 bars of
hydrogen pressure, the conversion reaches 93% after 6 hours, with a
selectivity to PAP of 92%. With a mixture of 0.01 g 1% Pt/C+0.5 g
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4-A5 and 20% bars of hydrogen
pressure, the conversion reaches 62% after 6 hours, with a
selectivity to PAP of 98%.
Examples B2-B8
Influence of the Amount of Catalyst
The platinum loading on the support has been changed to 0.1%, 0.5%,
1% and 2% using cationic exchange from Pt-amine, and the activity
measured at 80.degree. C., 3.8 bars hydrogen, with different
amounts of Pt/Zr(SO.sub.4).sub.2(H.sub.2O).sub.4 catalyst of
Example A5 (Zr(SO.sub.4).sub.2(H.sub.2O).sub.4-A5; 0.01, 0.1 and
0.3 g) with an amount of Zr(SO.sub.4).sub.2(H.sub.2O).sub.4-A5 of
0.1 g or 0.05 g. The catalytic results after 1 hour of reaction are
reported in Table 1 below:
TABLE-US-00003 TABLE 1 Zr(SO.sub.4).sub.2(H.sub.2O).sub.4- Pt
catalyst A5 NB AN PAP Example. # (g) % Pt (g) Conversion
Select.sup.(1) Select..sup.(2) B2 0.01 2.0 0.5 20.9 14.8 85.2 B3
0.01 1 0.1 10.3 3.3 96.7 B4 0.01 0.5 0.1 9.0 3.5 96.5 B5 0.03 0.5
0.1 28.0 2.5 97.5 B6 0.1 0.1 0.1 25.1 2.2 92.8 B7 0.1 0.1 0.05 8.6
2.5 97.5 (chlor).sup.(3) B8 0.1 0.1 0.05 20.7 14.9 85.1
.sup.(1)Selectivity to aniline (calculated as indicated above).
.sup.(2)Selectivity to PAP (calculated as indicated above).
.sup.(3)(chlor) = catalyst prepared from hexachloroplatinic
acid.
As a conclusion: Decreasing the amount of platinum from 1% to 0.5%
has no effect either on rate or selectivity; Increasing the amount
of Platinum catalyst from 0.01 g to 0.03 g increases the conversion
by 3, as expected, with a constant selectivity; A decrease of the
platinum loading to 0.1% induces an increase of activity. It is
assumed this increase is linked to a better dispersion of platinum
at low loading. This proposal is consistent with the observation of
a low activity of the catalyst prepared by wet impregnation from
the chloride salt. The comparison of Examples B6 and B8 shows that
an amount of zirconium sulfate of less than 0.1 g leads to a slight
loss of conversion and selectivity. With the lower amount of acid
catalyst, PHA appears in the products, probably because of the fact
that isomerisation is not fast enough to convert all the
intermediate.
Examples B9-B15
Influence of Zirconium Sulfate
Examples B9 to B15 have been conducted according to the process
described in Example B1, using a constant amount of 0.1 g of 2%
Pt/MgLaO, in association with various solid acid catalysts (0.5 g):
zirconia, sulphated titania (titanium dioxide), a HBEA zeolite, a
commercially available sulphated zirconia, and two zirconium
sulfates prepared as in Example A5
(Zr(SO.sub.4).sub.2(H.sub.2O).sub.4-A5) with two different
temperatures of calcination.
The results obtained after 1 hour reaction with 3 mL NB in 75 mL
water, 80.degree. C. and under 10 bars hydrogen pressure, are
listed in the below Table 2.
TABLE-US-00004 TABLE 2 Example NB Selectivity # Solid acid
conversion PHA PAP AN B9 ZrO.sub.2 922-1.sup.(4) 93.9 14.5 38 47.4
B10 Zr(SO.sub.4).sub.2(H.sub.2O).sub.4-A5 94.3 10 51.3 38.7 calc.
650.degree. C. B11 Zr(SO.sub.4).sub.2(H.sub.2O).sub.4-A5 97.2 0
76.1 23.9 calc. 625.degree. C. B12
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4-A5 79.2 0 95.3 4.7 calc.
550.degree. C. B13 Sulphated TiO.sub.2.sup.(5) 96.5 0.5 9.1 90.3
B14 Sulphated ZrO.sub.2 922-1 91.7 22.8 17.3 59.6 B15 HBEA
zeolite.sup.(6) 74.8 7 6.5 86.4 .sup.(4)supplied by MEL Chemicals
(Magnesium Electron, Inc.) .sup.(5)prepared by sulphation of a
titania gel supplied by Millenium Inorganic Chemicals.
.sup.(6)supplied by Zeolysts International (Si/Al = 25)
These results show that sulphated titania or HBEA zeolite is most
probably not enough acid to complete the Bamberger rearrangement.
Non-sulphated zirconia is inactive for this rearrangement (Example
B9), and the best PAP selectivity is obtained with a zirconium
sulfate prepared according to the process of the invention and
calcined at a temperature of 550-625.degree. C.
Isomerisation of Phenylhydroxylamine on Different Acid
Catalysts
The importance of the acidity of the solid acid is confirmed by the
separate study of the isomerisation of PHA to PAP, reported in
Table 3 below summarising the results obtained for the conversion
of PHA (prepared separately according to traditional procedures) at
80.degree. C.: 109 mg of PHA added to 7 mL of water were reacted in
the presence of 0.1 g of solid acid. The products are PAP,
o-aminophenol, aniline and nitrobenzene.
The results show that HBEA zeolite, K10 or bentonite are very
active but not selective for this reaction and form aniline and
other products. Moreover different zirconium sulfates show the same
high selectivity, but different conversion rates.
TABLE-US-00005 TABLE 3 Reaction Time PHA PAP Sample (min)
Conversion selectivity K10 (acid treated montmorillonite 30 100.0
17.6 from Sud Chemie) BEA zeolite 30 49.1 61.6 Bentonite-HPF 30
99.6 25.8 SiO.sub.2--SO.sub.3H.sup.(7) 30 78.0 94.2 Sulphated TiO2,
30 100 29.8 calc 50.degree. C. ZrS (from LOBA zirconia) 60 33.6
94.8 Zr(SO.sub.4).sub.2(H.sub.2O).sub.4-exZrOCl.sub.2 30 35.1 99.9
(calc 620.degree. C.) 60 47.3 96.8
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4 30 23.2 97.0 (calc 650.degree.
C.) 60 40.0 92.1 Zr(SO.sub.4).sub.2(H.sub.2O).sub.4-A5 30 100 99.6
calc 620.degree. C. ZrS Melcat 999-1 30 21.8 94.5 (calc 650.degree.
C.) 60 39.1 95.2 .sup.(7)for example conventionally obtained from
(MeO).sub.3Si-phenyl-SH oxidized with hydrogen peroxide.
Examples B16 and B17
Influence of the Amount of Platinum-Based Catalyst
Under the same conditions as in examples B9-B15, examples B16 and
B17 of preparation of PAP from NB have been conducted. In these
examples (1 hour reaction with 3 mL NB in 75 mL water, 80.degree.
C. and under 10 bars hydrogen pressure), the catalyst is a mixture
of 2% Pt/MgLaO (0.05 g and 0.01 g respectively) and 0.5 g of
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4-A5 (calcination: 5500).
The results are listed in the following Table 4.
TABLE-US-00006 TABLE 4 Amount NB Example # Pt/MgLaO conv. PHA PAP
AN Uks PAP sel. B16 0.05 g 98.9 0.0 7.8 90.5 0.6 7.9 B17 0.01 g
40.2 0.0 34.9 4.7 0.5 86.8
These results illustrate the fact that a high hydrogenation rate
leads to a fast conversion, but to aniline and not to PAP; using
the bi-functional catalyst supported platinum/zirconium sulfate,
care should be given to the balance of the two functions of
hydrogenation of NB to phenylhydroxylamine (PHA) and isomerisation
of PHA to PAP.
Example B18
Using 1% Pt/ZrO.sub.2 and Zirconium Sulfate of Example A5
Conversion of NB to PAP was conducted with the following
conditions:
TABLE-US-00007 NB amount: 3 mL; Water amount: 75 mL; Hydrogenation
catalyst: 0.02 g of 1% Pt/ZrO.sub.2 heated to 250.degree. C. (not
calcined); Zirconium sulfate: 1 g
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4-A5 calcined at 625.degree. C.;
Reaction time: 4 hours; Hydrogen pressure: 10 bars; and Reaction
temperature: 80.degree. C. The results are: NB conversion: 90.2;
and PAP selectivity: 85.2.
Example B19
Using 1% Pt/MgLaO and Zr(SO.sub.4).sub.2(H.sub.2O).sub.4-A5
Conversion of NB to PAP was conducted with the following
conditions:
TABLE-US-00008 NB amount: 3 mL; Water amount: 75 mL; Hydrogenation
catalyst: 0.02 g of 1% Pt/MgLaO heated to 250.degree. C. (not
calcined); Zirconium sulfate: 1 g
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4-A5 calcined at 625.degree. C.;
Reaction time: 4 hours; Hydrogen pressure: 10 bars; and Reaction
temperature: 80.degree. C. The results are: NB conversion: 80.2;
and PAP selectivity: 97.8.
Example B20
Using 2% Pt/MgLaO and Zr(SO.sub.4).sub.2(H.sub.2O).sub.4-A5
Conversion of NB to PAP was conducted with the following
conditions:
TABLE-US-00009 NB amount: 3 mL; Water amount: 75 mL; Hydrogenation
catalyst: 0.01 g of 2% Pt/MgLaO; Zirconium sulfate: 0.5 g
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4-A5 calcined at 625.degree. C.;
Reaction time: 4 hours; Hydrogen pressure: 10 bars; and Reaction
temperature: 80.degree. C. The results are: NB conversion: 97.2;
PAP selectivity: 76.1; PHA selectivity: 0; and Aniline selectivity:
23.9.
It should be noted that under the above conditions, no
phenylhydroxylamine was obtained, thereby facilitating the
separation PAP/aniline.
Example B21
Using 2% Pt/MgLaO and Zr(SO.sub.4).sub.2(H.sub.2O).sub.4-A5
Conversion of NB to PAP was conducted with the following
conditions:
TABLE-US-00010 NB amount: 25 mL; Water amount: 50 mL; Hydrogenation
catalyst: 0.1 g of 1% Pt/MgLaO; Zirconium sulfate: 1 g
Zr(SO.sub.4).sub.2(H.sub.2O).sub.4-A5 calcined at 625.degree. C.;
Reaction time: 2 hours; Hydrogen pressure: 10 bars; and Reaction
temperature: 80.degree. C. The results are: NB conversion: 29.8;
and PAP selectivity: 87.7.
In this experiment, concentration of NB is higher than in the
previous examples. No PHA was found in the reaction medium and a
good selectivity to PAP was obtained after 2 hours of reaction.
The above results also evidence a remarkable advantage of the use
and process of the invention: a small quantity of platinum is
sufficient to yield PAP with a good selectivity. Increasing the
amount of platinum in the mixture of catalysts is detrimental to
PAP selectivity.
The process of the invention therefore involves a cheap and
eco-friendly catalyst and is perfectly suited for industrial
applications, especially as an intermediate process to paracetamol
and other chemical, dyestuffs, and the like.
* * * * *